US7052802B2 - Fluorinated carbon active material - Google Patents

Fluorinated carbon active material Download PDF

Info

Publication number
US7052802B2
US7052802B2 US10/272,415 US27241502A US7052802B2 US 7052802 B2 US7052802 B2 US 7052802B2 US 27241502 A US27241502 A US 27241502A US 7052802 B2 US7052802 B2 US 7052802B2
Authority
US
United States
Prior art keywords
battery
wt
conductive material
positive electrode
cf
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US10/272,415
Other versions
US20040072075A1 (en
Inventor
Hisashi Tsukamoto
Kaname Takeya
Hiroyuki Yumoto
M. Elizabeth Bush
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quallion LLC
Original Assignee
Quallion LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Quallion LLC filed Critical Quallion LLC
Priority to US10/272,415 priority Critical patent/US7052802B2/en
Assigned to QUALLION LLC reassignment QUALLION LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAKEYA, KANAME, TSUKAMOTO, HISASHI, YUMOTO, HIROYUKI, BUSH, M. ELIZABETH
Publication of US20040072075A1 publication Critical patent/US20040072075A1/en
Application granted granted Critical
Publication of US7052802B2 publication Critical patent/US7052802B2/en
Application status is Active legal-status Critical
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/38Carbon pastes or blends; Binders or additives therein
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0421Methods of deposition of the material involving vapour deposition
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0421Methods of deposition of the material involving vapour deposition
    • H01M4/0423Physical vapour deposition
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0421Methods of deposition of the material involving vapour deposition
    • H01M4/0423Physical vapour deposition
    • H01M4/0426Sputtering
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0421Methods of deposition of the material involving vapour deposition
    • H01M4/0428Chemical vapour deposition
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0483Processes of manufacture in general by methods including the handling of a melt
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/06Electrodes for primary cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49108Electric battery cell making
    • Y10T29/49115Electric battery cell making including coating or impregnating

Abstract

Disclosed is an improved type of fluorinated carbon (CFx) for use in electrical storage devices such as batteries and capacitors. The CFx is coated with a conductive material such as gold or carbon using vapor deposition. The resulting material exhibits better conductivity with concomitant lower impedance, higher electrical stability, and improved potential throughout the useful life of the device, as compared to uncoated CFx. The improved conductivity reduces the amount of nonactive material (e.g., carbon black) that needs to be added, thus improving the volumetric energy density. In addition, cells made with the subject CFx exhibit more constant voltages and higher overall voltage (2.0 volts with a lithium metal anode) throughout their useful life. Chemical or physical vapor deposition techniques to deposit a variety of metals or carbon may be used to create the improved CFx. The coated CFx may be used in primary or secondary batteries, as well as capacitors and hybrid devices. Methods for making and using the coated CFx are described.

Description

REFERENCE TO PRIOR FILED APPLICATIONS

Not applicable

GOVERNMENT LICENSE RIGHTS

Not applicable

FIELD OF THE INVENTION

This invention relates to electrical storage cells, more particularly lithium batteries and capacitors using fluorinated carbon (CFx) as an electrode material. The method of the present invention significantly improves overall performance by increasing conductivity through the surface coating by deposition of conductive material.

BACKGROUND OF THE INVENTION

Fluorinated carbon (or Carbon Fluoride; hereinafter, CFx) has long been used in a CFx/Li primary battery as a Cathode. (See e.g., U.S. Pat. No. 3,536,532 to Watanabe.) It is a stable material; therefore, batteries containing a CFx cathode have low self-discharge rates and are stable over a wide range of temperatures. However, the material has relatively low electrical conductivity requiring a high amount of conductive additive such as carbon to comprise an electrode. Typically, a CFx electrode contains about 10 wt % of acetylene black (or other conductive additive), reducing a battery's volume energy density significantly.

The present invention fundamentally involves coating or depositing on the CFx particles a conductive material by means of vapor deposition, such as sputtering, laser ablation, or similar processes. This significantly reduces the amount of conductive additive, improves a CFx cathode's volume energy density, improves CFx's high rate discharge capability, and exhibits more stable electrical characteristics.

SUMMARY OF THE INVENTION

The CFx cathode made by the method of the present invention has deposited on it a conductive material (carbon and/or metal) by means of vapor deposition (e.g., sputtering, or laser ablation), nominally at room temperature, to below 650° C. The deposition may take place in a vacuum atmosphere, a low-pressure inert gas atmosphere (e.g., argon) or under pressure to about 10 atmospheres. The deposition process uses a carbonaceous organic vapor to deposit carbon and/or metallized carbonaceous organic vapor to deposit metal with or without carbon, or an inert atmosphere (e.g., argon). A follow-on heat treatment may also be employed at temperatures up to around 650° C. However, the best mode of the present invention does not require such treatment.

Vapor deposition in a vacuum or low pressure argon gas results in the CFx being surface coated. Vapor deposition in a pressurized atmosphere (and optionally at elevated temperatures to about 650° C.) forces the conductive material into the CFx particle.

CFx materials are known in the art, and are commercially available, for example, from Daikin Industries, LTD, Japan. Various processes are used to produce CFx, with some being described as “high temperature”, or “HT”, and some being “low temperature”, or “LT”. Examples of each can be found described in U.S. Pat. Nos. 5,712,062 and 6,068,921 to Yamana et al, assigned to Daikin Industries, Ltd., Osaka, Japan, and in U.S. Pat. No. 6,358,649 to Yazami et al., entitled, “Carbons containing fluorine, method of preparation thereof and use as electrode material,” all of which are hereby incorporated herein by reference in their entirety. The material of Yazami et al. is reportedly more conductive that other types known in the art, and therefore may be preferred for use in the present invention.

TABLE 1 Candidate Elements Most Preferred Ag (6.21)*, Au (4.55), Rh (2.08), Ir (1.96) Pt (.96) Pd (.95), C (0.2) Less Preferred Cu (5.88), Al (3.65), Be (3.08), Ca (2.78), Mg (2.33), W (1.89), Mo (1.89), Co (1.72), Zn (1.69), Ni (1.43), Cd (1.38), Ru (1.35), In (1.14), Os (1.1), Fe (1.02), Fe (1.02) Sn (0.91), Cr (0.78), Ta (0.76), Tc (0.7), Nb (0.69), Ga (0.67), TL (0.61), Re (0.54), V (0.5), Pb (0.48), Sr (0.47), Si (0.42), Hf (0.33), Ba (0.26), Zr (0.24), Sb (0.24), Ti (0.23), Po (0.22), Sc (0.21), Y (0.17), Lu (0.13). *Numbers in parentheses are conductivity: 105 (Ωcm)−1

Normally, where a metal is used, gold is preferred, but other conductive materials such as shown in Table 1 and mixtures or alloys thereof may be substituted or added. Preferred deposition materials are gold, silver, platinum, rhodium, palladium, iridium, and carbon which have low contact resistance. Alloys of the most preferred metals are possible, and superior to use of the less-preferred materials. Standard, well-known coating or deposition techniques may be utilized including both chemical and physical deposition, coating, argon sputtering, vacuum sputtering, laser ablation, or similar processes. Low temperature vapor deposition may be utilized in which a carbonaceous gas, such as acetylene, is heated to deposit carbon onto CFx particles. Metals that have a tendency for high surface oxidation may be coated with lower oxidizing metals. For example, copper or aluminum may be deposited, followed by gold to maintain high surface conductivity. The conductive layer deposited on the CFx may be metallic or carbon, and can be a porous film or dispersed, discrete island structures. As used herein, “coat” or “coating” shall include all deposition conformations or distributions, whether contiguous or dispersed, regardless of the proportion of surface being covered.

The inventors have found cells made utilizing gold coated CFx exhibit lower internal resistance, higher overall voltage, and much more stable voltage characteristics. Furthermore, vapor-depositing the conductive material onto CFx requires less conductive material but provides better contact than simply mixing conductive additive power with CFx.

The same cathode of the present invention may also be advantageously used in secondary cells, capacitors, and in devices combining features of capacitors and electrical storage cells.

A wide variety of electrolyte salts may advantageously be used, including LiPF6 or Lithium bis(oxalato)borate (LiBOB).

OBJECTIVES OF THE INVENTION

Accordingly, it is an objective to provide an electrochemical storage device with reduced internal impedance.

It is a further objective to provide an electrochemical storage device which exhibits relatively constant voltage during discharge.

It is a further objective to provide an electrochemical storage device with increased volumetric energy density.

Other features and advantages of the invention will be apparent from the claims, and from the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of discharge voltage profile of a test cell made according to the present invention compared with a reference cell.

DETAILED DESCRIPTION

The present invention resulted from the discovery that coating CFx with conductive material, rather than mixing it with such material as carbon, improved its electrical characteristics, including increased conductivity, increased volume energy density, more constant discharge voltages, and higher overall voltage. A better understanding of the invention may be obtained by review of the following specific example.

EXAMPLE

A sandwich type gold coated CFx cell and a reference sandwich type conventional CFx cell were produced in accordance with the invention. The test cell cathode material was prepared by argon sputtering deposition of gold on CFx. The deposition was carried out as follows:

1. A glass plate with 1.6 g CFx powder was placed in a vacuum chamber.

2. The vacuum chamber was evacuated to approximately 50–80 millitorr.

3. The chamber was flushed with argon gas.

4. The vacuum chamber was filled with Ar gas. Pressure was kept at 80 millitorr.

5. 7–8.5 volts was applied to the Ar gas to form a plasma.

6. The plasma hit a gold plate to generate Au vapor. Plasma current was kept around 15 milliamperes.

7. The gold was permitted to deposit on the CFx powder five times for 3 minutes each time. Between each sputtering deposition interval, the powder was agitated.

The CFx so prepared was then used in assembling the test cell. The reference cell was prepared in every respect in the same way, except there was no deposition of gold or other conductive material on the CFx.

The anode in both cells was pure lithium metal with Cu substrate. The electrolyte was a salt consisting of 1.2 molar LiPF6 in 25 wt % EC, 75 wt % DEC and a cathode according to the following composition:

CFx (+ Au): 85 wt % PTFE:  3 wt % CMC  2 wt % Acetylene Black: 10 wt %.

The above electrode composition is believed by the inventors to constitute the best mode of the present invention. The use of argon sputtering is believed to be the best mode for depositing the conductive material (gold) onto the CFx.

The above components were mixed with a solvent and coated on a 20 μm aluminum substrate. The solvent was then evaporated at 80° C. leaving the cathode composed of the listed components which was then calendared to the desired thickness. Calendaring or pressing is commonly used to compress the material and adhere it to the substrate. As used herein, “compressing” shall include all methods of applying pressure, including calendaring and pressing.

The CFx used in the above example was obtained from Daikin Industries, LTD, and was Grade number CF-GM, wherein x=0.9–1.1.

It was found that utilizing a combination of two binders polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC)) resulted in improved stability of the viscosity of the coating paste during the coating process. This improves manufacturability by improving the nature of the coating for better handling. Specifically, the coating paste maintains the same viscosity throughout the coating process. The binders are individually well-known in the art, but combining them in a single cathode showed surprisingly beneficial results with regard to the consistency and manufacturability of the electrode material. Other binders may be substituted or added, including polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), and styrene butadiene rubber (SBR). Similarly, other substrates besides aluminum may be used, including but not limited to stainless steel, titanium, and alloys thereof, with aluminum and stainless steel being preferred. Based on the data presented below, the conductive additive (e.g., acetylene black) content may be reduced to about 1 wt % to about 5 wt %, which is 2 to 10 volume %, significantly increasing volumetric energy density while maintaining adequate conductivity. Other types of carbon black or other conductive materials such as graphite may be substituted for acetylene black, or added to it. The inventors have noted that the amount of binder required is partly dependent on the amount of conductive additive used; because of the large surface area of the conductive additive, if the amount of conductive additive is reduced from 10 wt % to about 5 wt %, the total amount of binder may be reduced from 5 wt % to between 1 and 3 wt %.

FIG. 1 shows the comparative results of pulse discharge testing of both cells. Pulse discharge testing of test cells made according to the present method and reference cells made without deposition of a conductive material on the CFx cathode over approximately 1000 minutes (60,000 seconds) of 0.005 C with a discharge pulse of 0.5 C for 10 ms at every 10 minutes (600 seconds) demonstrated the highly beneficial effects of the present invention. The two lower traces 100 and 104 represent the respective voltages measured during each 0.5 C pulse discharge (“pulse discharge voltage”). Trace 100 is the pulse discharge voltage of the cell with untreated CFx. Trace 104 is the pulse discharge voltage of the cell with gold-coated CFx. The upper traces 108 and 112 represent the respective cell voltages during the 10-minute 0.005 C discharge (“normal discharge voltage”). Trace 108 is the normal discharge voltage of the cell with untreated CFx. Trace 112 is the normal discharge voltage of the cell having a gold-coated CFx cathode. It may be seen that the reference cells (no gold) exhibited about 0.7 V or more drop during each pulse discharge, while the test cells (with gold) dropped only about 0.5 V. Moreover, the reference battery voltage in the reference cell initially dropped from about 3.25 V to about 2.5 V and gradually climbed back to a peak of about 2.6 V over the first 25,000 seconds before it began to drop off gradually to 2.5 V over the course of the pulse discharge. This is compared to the test cell (with gold) which exhibited a much more stable discharge curve, spiking down from 3.25 V in the first discharge to 2.75 V, then gradually decaying to a minimum of 2.6 V over about 25,000 seconds and stabilizing to almost a flat line. This much more stable discharge voltage profile is highly beneficial, particularly in medical applications.

Significantly, during each 0.5 C pulse discharge, the reference cells voltages dropped to 1.7 V to 1.9 V. The test cells (with gold deposited on CFx) dropped to a minimum of 2.1 V to 2.2 V. Therefore, cells made according to the present method will operate devices requiring a 2.0 V minimum, as the cells will maintain at least 2.0 volts throughout their useful life. The present invention is particularly suited to medical devices, notably implanted batteries where stability, longevity, safety are paramount, and where changing primary batteries requires surgical intervention.

The CFx of the present invention may also be mixed with other active materials. An “active material” is a chemically reactive material at the positive or negative electrode that takes part in the charge and discharge reactions. In a lithium battery positive electrode, it can be any material capable of absorbing lithium ions. Such materials are well-known to those skilled in the art. Mixing of two or more active materials may be used to improve better end-of-life indication. See e.g., U.S. Pat. No. 5,667,916 issued to Ebel et al. disclosing using two mixed cathode materials, each with a discrete voltage characteristic. In the present invention, mixing of a second or additional active material may be done before or after treating the CFx powder with a conductive coating. If treated after mixing, the entire mixture of powders may receive beneficial results. The second or more active materials should be in an amount less than that of the CFx, and preferably less than about 20 wt % of the CFx.

It should be noted that others have deposited metals onto the negative active material, graphite, to accelerate the electrochemical rates of inter- and de-intercalation of Li in the substrate carbon. See e.g., Suzuki et al., “Li Mass Transfer through a Metallic Copper Film on a Carbon Fiber During the Electrochemical Insertion/Extraction Reaction,” Electrochemical and Solid State Letters, 4(1)A1–A4 (2001) and Momose et al., “X-ray Photoelectron Spectroscopy Analysis of Lithium Intercalation and Alloying Reactions on Graphite Electrodes,” J. Power Sources 209–211 (1997). In contrast, the method of the present invention, and active electrode material produced thereby, solves a different problem, that problem being high contact resistance in the positive active material, CFx. CFx is a very different material from graphite, and the reaction of Li ion with CFx is not an intercalation reaction. Li ions do not intercalate into CFx; Li ions simply react with CFx and create LiF. The present invention does not assist in lithium ion intercalation, but only reduces the contact resistance of CFx.

From the foregoing, it is apparent that the processes provided by the invention enable production of superior-performing electrochemical storage devices that are characterized by relatively stable voltage over their lifetime, improved internal conductivity (and concomitant reduced internal impedance), and improved volumetric energy density (as compared with prior art). The invention thereby provides the ability to produce, among other things, storage cells capable of powering devices requiring 2.0 V minimum operating voltage. The devices are particularly suited to medical applications, notably implantable medical devices.

The specific implementations disclosed above are by way of example and for enabling persons skilled in the art to implement the invention only. We have made every effort to describe all the embodiments we have foreseen. There may be embodiments that are unforeseeable and which are insubstantially different. We have further made every effort to describe the methodology of this invention, including the best mode of practicing it. Any omission of any variation of the method disclosed is not intended to dedicate such variation to the public, and all unforeseen, insubstantial variations are intended to be covered by the claims appended hereto. Accordingly, the invention is not to be limited except by the appended claims and legal equivalents.

Claims (27)

1. A battery, comprising:
a negative electrode;
a positive electrode operatively associated with the negative electrode;
electrolyte activating the negative electrode and the positive electrode;
the positive electrode including a Carbon Fluoride (CFx) coated with a layer of a conductive material, the layer being in accordance with vapor deposition of the conductive material on the Carbon Fluoride (CFx).
2. The battery of claim 1, wherein the conductive material includes at least one component selected from the group consisting of: carbon, rhodium, palladium, silver, iridium, platinum, gold, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, technetium, rhenium, iron, ruthenium, osmium, cobalt, nickel, copper, zinc, cadmium, aluminum, gallium, indium, thallium, silicon, tin, lead, antimony, and polonium.
3. The battery of claim 1, wherein the conductive material is vapor deposited on the Carbon Fluoride.
4. The battery of claim 1, wherein the conductive material comprises a porous film.
5. The battery of claim 1, wherein the conductive material comprises discrete islands.
6. The battery of claim 1, wherein the positive electrode further includes at least one active material in addition to the Carbon Fluoride.
7. The battery of claim 6, wherein the at least one additional active material is present in the positive electrode in a proportion less than that of the Carbon Fluoride by weight.
8. The battery of claim 6, wherein the at least one additional active material is present in the positive electrode in a proportion less than about 20% of the Carbon Fluoride by weight.
9. The battery of claim 1, wherein the primary battery voltage during discharge is at least 2.0 volts throughout a useful life of the battery.
10. The battery of claim 1, wherein the positive electrode further includes a mixture of at least two binders.
11. The battery of claim 10, wherein the at least two binders are selected from the group consisting of: polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), and styrene butadiene rubber (SBR).
12. The battery of claim 10, wherein at least one of the at least two binders is selected from the group consisting of polytetrafluoroethylene (PTFE), and carboxymethyl cellulose (CMC).
13. The battery of claim 10, wherein the positive electrode includes up to about 1 wt % to about 5 wt % total binder.
14. The battery of claim 10, wherein the positive electrode includes about 85 wt % Carbon Fluoride with conductive material deposited thereon, about 10 wt % conductive additive, and about 1 wt % to about 5 wt % binder.
15. The battery of claim 10, wherein the positive electrode includes about 90 wt % to about 94 wt % Carbon Fluoride with conductive material deposited thereon, about 1 wt % to about 5 wt % conductive additive, and about 1 wt % to about 5 wt % binder.
16. The battery of claim 14, wherein the conductive additive includes carbon.
17. The battery of claim 15, wherein the conductive additive includes carbon.
18. The battery of claim 2, wherein the conductive material includes at least two of the components arranged in a first and a second layer,
the first layer including a first of the at least two components, and
the second layer including a second of the at least two components.
19. The battery of claim 1, wherein the Carbon Fluoride is at least 80 wt % of the positive electrode.
20. The battery of claim 1, wherein the Carbon Fluoride and conductive material is at least 85 wt % of the positive electrode.
21. The battery of claim 1, wherein the positive electrode includes:
about 85 wt % of the Carbon Fluoride having a conductive material deposited thereon;
about 10 wt % conductive additive; and
about 1 wt % to about 5 wt % of one or more binders.
22. The battery of claim 1, wherein the positive electrode includes:
about 90 wt % to about 94 wt % Carbon Fluoride with conductive material deposited thereon;
about 1 wt % to about 5 wt % conductive additive; and
about 1 wt % to about 5 wt % binder.
23. The battery of claim 1, wherein the conductive material includes a metal.
24. The battery of claim 23, wherein the conductive material consists of a metal.
25. The battery of claim 1, wherein the layer of conductive material is adhered directly to the Carbon Fluoride (CFx).
26. The battery of claim 1, wherein the layer of the conductive material consists of the conductive material.
27. The battery of claim 1, wherein the layer of the conductive material is a film of the conductive material.
US10/272,415 2002-10-15 2002-10-15 Fluorinated carbon active material Active 2023-12-09 US7052802B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/272,415 US7052802B2 (en) 2002-10-15 2002-10-15 Fluorinated carbon active material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/272,415 US7052802B2 (en) 2002-10-15 2002-10-15 Fluorinated carbon active material
US11/387,622 US7503943B2 (en) 2002-10-15 2006-03-22 Fluorinated carbon active material

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/387,622 Continuation US7503943B2 (en) 2002-10-15 2006-03-22 Fluorinated carbon active material

Publications (2)

Publication Number Publication Date
US20040072075A1 US20040072075A1 (en) 2004-04-15
US7052802B2 true US7052802B2 (en) 2006-05-30

Family

ID=32069260

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/272,415 Active 2023-12-09 US7052802B2 (en) 2002-10-15 2002-10-15 Fluorinated carbon active material
US11/387,622 Active 2023-07-30 US7503943B2 (en) 2002-10-15 2006-03-22 Fluorinated carbon active material

Family Applications After (1)

Application Number Title Priority Date Filing Date
US11/387,622 Active 2023-07-30 US7503943B2 (en) 2002-10-15 2006-03-22 Fluorinated carbon active material

Country Status (1)

Country Link
US (2) US7052802B2 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060172202A1 (en) * 2005-02-03 2006-08-03 Smith W N Low temperature electrolytes and cell construction for low temperature lithium rechargeable batteries
US20070270927A1 (en) * 2006-05-19 2007-11-22 Greatbatch Ltd. Method For Producing Implantable Electrode Coatings With A Plurality Of Morphologies
US20090029237A1 (en) * 2005-10-05 2009-01-29 Rachid Yazami Fluoride ion electrochemical cell
US20100021800A1 (en) * 2008-07-24 2010-01-28 Rachid Yazami Carbon cathodes for fluoride ion storage
US20100068609A1 (en) * 2008-09-15 2010-03-18 Ultralife Corportion Hybrid cell construction for improved performance
US20100221603A1 (en) * 2006-03-03 2010-09-02 Rachid Yazami Lithium ion fluoride battery
US20140090977A1 (en) * 2011-09-29 2014-04-03 Alan Boardman Lead-Free Oxygen Sensor
US8961833B2 (en) 2010-11-24 2015-02-24 The United States Of America As Represented By The Secretary Of The Army Fluorinated carbon composite cathode for a high-energy lithium battery

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7632317B2 (en) * 2002-11-04 2009-12-15 Quallion Llc Method for making a battery
JP2005026349A (en) * 2003-06-30 2005-01-27 Tdk Corp Method for manufacturing electrochemical capacitor and electrode therefor
US8524397B1 (en) 2004-11-08 2013-09-03 Quallion Llc Battery having high rate and high capacity capabilities
US8685568B2 (en) * 2006-02-01 2014-04-01 Greatbatch Ltd. Lithium/fluorinated carbon cell for high-rate pulsatlie applications
US20070292600A1 (en) * 2006-06-19 2007-12-20 Morgan Adam J Pressed powder pellet battery electrode system
WO2009014845A2 (en) * 2007-06-28 2009-01-29 Ultralife Corporation High capacity and high rate lithium cells with cfx-mno2 hybrid cathode
JP5515476B2 (en) * 2009-07-16 2014-06-11 ソニー株式会社 Secondary battery, negative electrode, positive electrode and electrolyte
US9130229B2 (en) * 2013-01-02 2015-09-08 Medtronic, Inc. Carbon fluoride cathodes and batteries made therefrom
US9771539B2 (en) * 2013-02-06 2017-09-26 Daikin Industries, Ltd. Solid particle, solid lubricant, and metal member
CN104577107B (en) * 2013-10-14 2018-01-16 中国电子科技集团公司第十八研究所 A kind of surface modification method of fluorinated carbon material
EP3167501B1 (en) 2014-07-08 2018-08-29 Cardiac Pacemakers, Inc. Method to stabilize lithium / carbon monofluoride battery during storage
KR101882975B1 (en) * 2016-04-21 2018-07-27 주식회사 비츠로셀 Method for menufacturing a cathode of lithium primary battery

Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514337A (en) 1968-06-06 1970-05-26 Us Navy High energy density battery
US3536532A (en) 1968-04-12 1970-10-27 Matsushita Electric Ind Co Ltd Primary cell for electric batteries
US3892590A (en) 1973-07-16 1975-07-01 Yardney International Corp Cathode material for use in non-aqueous electrolytes
US3922174A (en) 1973-01-22 1975-11-25 Gte Laboratories Inc Electrochemical cell
US4163829A (en) 1977-11-14 1979-08-07 Union Carbide Corporation Metallic reducing additives for solid cathodes for use in nonaqueous cells
JPS58128657A (en) 1982-01-26 1983-08-01 Matsushita Electric Ind Co Ltd Battery
JPS5983353A (en) 1982-11-04 1984-05-14 Matsushita Electric Ind Co Ltd Manufacture of battery
JPS61117503A (en) 1984-11-14 1986-06-04 Shinku Kikai Kogyo Kk Formation of fluoride film
JPS62188168A (en) 1986-02-14 1987-08-17 Denki Kagaku Kogyo Kk Lithium battery
JPS6489144A (en) 1987-09-30 1989-04-03 Toshiba Corp Composite material
US4863814A (en) 1986-03-27 1989-09-05 Sharp Kabushiki Kaisha Electrode and a battery with the same
US4931240A (en) 1987-09-19 1990-06-05 Sharp Kabushiki Kaisha Method for the production of a carbon electrode
US4967025A (en) * 1988-07-11 1990-10-30 Daikin Industries, Ltd. Purification method of carbon fluorides
US5175066A (en) 1988-12-26 1992-12-29 Centre National De La Recherche Scientifique (Cnrs) Rechargeable battery with solid electrolyte
US5180642A (en) 1992-02-24 1993-01-19 Medtronic, Inc. Electrochemical cells with end-of-service indicator
JPH0547385A (en) 1991-08-20 1993-02-26 Sanyo Electric Co Ltd Secondary battery
JPH07335263A (en) 1994-06-10 1995-12-22 Tdk Corp Lithium secondary battery
US5667916A (en) 1996-05-10 1997-09-16 Wilson Greatbatch Ltd. Mixed cathode formulation for achieving end-of-life indication
WO1997041061A1 (en) 1996-04-26 1997-11-06 Centre National De La Recherche Scientifique New carbons containing fluorine, method of preparation thereof and use as electrode material
US5712062A (en) 1992-11-06 1998-01-27 Daikin Industries, Ltd. Carbon fluoride particles, preparation process and uses of the same
US5716466A (en) 1993-12-20 1998-02-10 Shinko Kosen Kogyo Kabushiki Kaisha Stainless steel wire product
JPH10275619A (en) 1997-03-31 1998-10-13 Shin Kobe Electric Mach Co Ltd Paste type cadmium electrode
EP0886332A1 (en) 1997-06-19 1998-12-23 Matsushita Electric Industrial Co., Ltd. Nonaqueous secondary lithium battery with a negative electrode comprising (CF)n
JP2000067905A (en) 1998-08-25 2000-03-03 Toshiba Battery Co Ltd Secondary battery
US6211065B1 (en) 1997-10-10 2001-04-03 Applied Materials, Inc. Method of depositing and amorphous fluorocarbon film using HDP-CVD
US6332900B1 (en) 1999-02-08 2001-12-25 Wilson Greatbatch Ltd. Physical vapor deposited electrode component and method of manufacture
JP2002063894A (en) 2000-08-22 2002-02-28 Nobuyuki Koura Production method of carbon material film, and nonaqueous secondary battery using the carbon material film
JP2002141058A (en) 2000-11-06 2002-05-17 Nec Corp Lithium secondary battery and its manufacturing method
US20020098410A1 (en) 1999-07-30 2002-07-25 Cochlear Limited Secondary electrochemical cell
US6589696B2 (en) 2000-06-16 2003-07-08 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery and method of preparing same
US20030138697A1 (en) 2002-01-24 2003-07-24 Randolph Leising Cathode active material coated with a metal oxide for incorporation into a lithium electrochemical cell
US20030138698A1 (en) 2002-01-17 2003-07-24 Korea Institute Of Science And Technology Carbonaceous materials coated with a metal or metal oxide, a preparation method thereof, and a composite electrode and lithium secondary battery comprising the same
US20040163235A1 (en) * 2001-06-20 2004-08-26 Hans Feil Method of manufacturing a lithium battery as well as a lithium battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3890185B2 (en) * 2000-07-27 2007-03-07 公立大学法人大阪市立大学 Positive electrode active material and non-aqueous electrolyte secondary battery including the same

Patent Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536532A (en) 1968-04-12 1970-10-27 Matsushita Electric Ind Co Ltd Primary cell for electric batteries
US3514337A (en) 1968-06-06 1970-05-26 Us Navy High energy density battery
US3922174A (en) 1973-01-22 1975-11-25 Gte Laboratories Inc Electrochemical cell
US3892590A (en) 1973-07-16 1975-07-01 Yardney International Corp Cathode material for use in non-aqueous electrolytes
US4163829A (en) 1977-11-14 1979-08-07 Union Carbide Corporation Metallic reducing additives for solid cathodes for use in nonaqueous cells
JPS58128657A (en) 1982-01-26 1983-08-01 Matsushita Electric Ind Co Ltd Battery
JPS5983353A (en) 1982-11-04 1984-05-14 Matsushita Electric Ind Co Ltd Manufacture of battery
JPS61117503A (en) 1984-11-14 1986-06-04 Shinku Kikai Kogyo Kk Formation of fluoride film
JPS62188168A (en) 1986-02-14 1987-08-17 Denki Kagaku Kogyo Kk Lithium battery
US4863814A (en) 1986-03-27 1989-09-05 Sharp Kabushiki Kaisha Electrode and a battery with the same
US4931240A (en) 1987-09-19 1990-06-05 Sharp Kabushiki Kaisha Method for the production of a carbon electrode
JPS6489144A (en) 1987-09-30 1989-04-03 Toshiba Corp Composite material
US4967025A (en) * 1988-07-11 1990-10-30 Daikin Industries, Ltd. Purification method of carbon fluorides
US5175066A (en) 1988-12-26 1992-12-29 Centre National De La Recherche Scientifique (Cnrs) Rechargeable battery with solid electrolyte
JPH0547385A (en) 1991-08-20 1993-02-26 Sanyo Electric Co Ltd Secondary battery
US5180642A (en) 1992-02-24 1993-01-19 Medtronic, Inc. Electrochemical cells with end-of-service indicator
US6068921A (en) 1992-11-06 2000-05-30 Daikin Industries, Ltd. Carbon fluoride particles, preparation process and users of the same
US5712062A (en) 1992-11-06 1998-01-27 Daikin Industries, Ltd. Carbon fluoride particles, preparation process and uses of the same
US5716466A (en) 1993-12-20 1998-02-10 Shinko Kosen Kogyo Kabushiki Kaisha Stainless steel wire product
JPH07335263A (en) 1994-06-10 1995-12-22 Tdk Corp Lithium secondary battery
US6358649B1 (en) 1996-04-26 2002-03-19 Centre National De La Recherche Scientifique Carbons containing fluorine, method of preparation thereof and use as electrode material
EP0910547B1 (en) 1996-04-26 2001-07-04 Centre National De La Recherche Scientifique (Cnrs) New carbons containing fluorine, method of preparation thereof and use as electrode material
WO1997041061A1 (en) 1996-04-26 1997-11-06 Centre National De La Recherche Scientifique New carbons containing fluorine, method of preparation thereof and use as electrode material
US5667916A (en) 1996-05-10 1997-09-16 Wilson Greatbatch Ltd. Mixed cathode formulation for achieving end-of-life indication
JPH10275619A (en) 1997-03-31 1998-10-13 Shin Kobe Electric Mach Co Ltd Paste type cadmium electrode
EP0886332A1 (en) 1997-06-19 1998-12-23 Matsushita Electric Industrial Co., Ltd. Nonaqueous secondary lithium battery with a negative electrode comprising (CF)n
US6211065B1 (en) 1997-10-10 2001-04-03 Applied Materials, Inc. Method of depositing and amorphous fluorocarbon film using HDP-CVD
JP2000067905A (en) 1998-08-25 2000-03-03 Toshiba Battery Co Ltd Secondary battery
US6332900B1 (en) 1999-02-08 2001-12-25 Wilson Greatbatch Ltd. Physical vapor deposited electrode component and method of manufacture
US20020041997A1 (en) 1999-02-08 2002-04-11 Muffoletto Barry C. Electrochemical cell having a physical vapor deposited electrode and method of manufacture
US20020098410A1 (en) 1999-07-30 2002-07-25 Cochlear Limited Secondary electrochemical cell
US6589696B2 (en) 2000-06-16 2003-07-08 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery and method of preparing same
JP2002063894A (en) 2000-08-22 2002-02-28 Nobuyuki Koura Production method of carbon material film, and nonaqueous secondary battery using the carbon material film
JP2002141058A (en) 2000-11-06 2002-05-17 Nec Corp Lithium secondary battery and its manufacturing method
US20040163235A1 (en) * 2001-06-20 2004-08-26 Hans Feil Method of manufacturing a lithium battery as well as a lithium battery
US20030138698A1 (en) 2002-01-17 2003-07-24 Korea Institute Of Science And Technology Carbonaceous materials coated with a metal or metal oxide, a preparation method thereof, and a composite electrode and lithium secondary battery comprising the same
US20030138697A1 (en) 2002-01-24 2003-07-24 Randolph Leising Cathode active material coated with a metal oxide for incorporation into a lithium electrochemical cell

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
Croce et al., A Novel Concept for the Synthesis of an Improved LifePO<SUB>4 </SUB>Lithium Battery Cathode, Electrochemical and Solid-State Letters, 2002, A47-A50, 5(3).
Endo et al.; Discharge characteristics of a lithium battery with fibrous carbon fluoride; Dialog Abstract for Elsevier; Journal of Power Sources; vol. 20, No. 1-2; pp. 99-104; 1987; Switzerland.
Endo et al.; Lithium primary battery with high electrical potential using fluorinated graphite fibers of second-stage intercalation; Dialog Abstract for Elsevier; Electrical Engineering in Japan; Col. 110, No. 7; pp. 13-21; 1990; US.
Fahys et al.; Lithium nitrate and lithium trifluoromethanesulfonate ammoniates fro electrolytes in lithium batteries; Dialog Abstract for Elsevier; Journal of Power Sources; vol. 34, No. 2; pp. 183-188; 1991; Switzerland.
Kim et al.; Electrochemical performance of natural graphite by surface modification using aluminum; Electrochemical and Solid State Letters; vol. 4(8); pp. A109-A112; 2001.
Momose et al.; X-ray photoelectron spectroscopy analyses of lithium intercalation and alloying reaction son graphite electrodes; Journal of Power Sources; vol. 68; pp. 208-211; 1997.
Ping et al.; Fabrication of LiV/sub2/O/sub 5/ thin-film electrodes for rechargeable lithium batteries; Dialog Abstract for Elsevier; Solid State Ionics; Col. 111, No. 1-2; pp. 145-151; 1998; Netherlands.
Suzuki et al.; Li mass transfer through a metallic copper film on a carbon fiber during the electrochemical insertion/extraction reaction; Electrochemical and Solid State Letters; vol. 4(1); pp. A1-A4; 2001.

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060172202A1 (en) * 2005-02-03 2006-08-03 Smith W N Low temperature electrolytes and cell construction for low temperature lithium rechargeable batteries
US20090029237A1 (en) * 2005-10-05 2009-01-29 Rachid Yazami Fluoride ion electrochemical cell
US8968921B2 (en) 2005-10-05 2015-03-03 California Institute Of Technology Fluoride ion electrochemical cell
US8377586B2 (en) 2005-10-05 2013-02-19 California Institute Of Technology Fluoride ion electrochemical cell
US20100221603A1 (en) * 2006-03-03 2010-09-02 Rachid Yazami Lithium ion fluoride battery
US20070270927A1 (en) * 2006-05-19 2007-11-22 Greatbatch Ltd. Method For Producing Implantable Electrode Coatings With A Plurality Of Morphologies
US8948881B2 (en) 2006-05-19 2015-02-03 Greatbatch Ltd. Method for producing implantable electrode coatings with a plurality of morphologies
US20100021800A1 (en) * 2008-07-24 2010-01-28 Rachid Yazami Carbon cathodes for fluoride ion storage
US20100068609A1 (en) * 2008-09-15 2010-03-18 Ultralife Corportion Hybrid cell construction for improved performance
US8961833B2 (en) 2010-11-24 2015-02-24 The United States Of America As Represented By The Secretary Of The Army Fluorinated carbon composite cathode for a high-energy lithium battery
US20140090977A1 (en) * 2011-09-29 2014-04-03 Alan Boardman Lead-Free Oxygen Sensor
US9146208B2 (en) * 2011-09-29 2015-09-29 Brigham Young University Lead-free oxygen sensor

Also Published As

Publication number Publication date
US20060162150A1 (en) 2006-07-27
US7503943B2 (en) 2009-03-17
US20040072075A1 (en) 2004-04-15

Similar Documents

Publication Publication Date Title
EP0690517B1 (en) Rechargeable lithium battery
US5487959A (en) Layer for stabilization of lithium anode
ES2405600T3 (en) Carbon-coated silicon particle powder as the anode material for lithium-ion batteries and their preparation method
EP1033767B1 (en) Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary cell
US9356281B2 (en) Intercalation electrode based on ordered graphene planes
US8216720B2 (en) Negative electrode for lithium secondary cell and lithium secondary cell
CA2345518C (en) Sandwich cathode design for alkali metal electrochemical cell with high discharge rate capability
JP4445465B2 (en) Carbon-coated aluminum and method for producing the same
JP3619000B2 (en) Electrode structure, a secondary battery and a process for their preparation
US6413672B1 (en) Lithium secondary cell and method for manufacturing the same
US20020168574A1 (en) Lithium ion secondary battery and manufacturing method of the same
US20050084756A1 (en) Nonaqueous electrochemical cell with improved energy density
US20060003226A1 (en) Lithium secondary battery and method for producing same
CN100490220C (en) Negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode
US7459235B2 (en) Anode composition for lithium battery, and anode and lithium battery using the same
DE60309815T2 (en) Lithium-ion battery with inorganic Li-ion conducting solid electrolyte
KR100599602B1 (en) Positive electrode for lithium secondary battery and lithium secondary battery comprising the same
CN100570929C (en) Anode and battery using the same
EP0741426B1 (en) Manufacturing method for electrode
DE60202783T2 (en) Electrode compositions with improved loading unloading behavior
EP1711971B1 (en) Electrode additives coated with electro conductive material and lithium secondary comprising the same
JP3676301B2 (en) The electrode for a lithium secondary battery and lithium secondary battery
US5436093A (en) Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell
KR100661402B1 (en) Electrode material for rechargeable lithium battery, electrode structural body comprising said electrode material, rechargeable lithium battery having said electrode structural body, process for the production of said electrode structural body, and process for the production of said rechargeable lithium battery
JPWO2006011290A1 (en) SiO powder for secondary battery and method for producing the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: QUALLION LLC, CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TSUKAMOTO, HISASHI;TAKEYA, KANAME;YUMOTO, HIROYUKI;AND OTHERS;REEL/FRAME:013564/0741;SIGNING DATES FROM 20021016 TO 20021023

STCF Information on status: patent grant

Free format text: PATENTED CASE

REMI Maintenance fee reminder mailed
SULP Surcharge for late payment
FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
FPAY Fee payment

Year of fee payment: 8

SULP Surcharge for late payment

Year of fee payment: 7

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553)

Year of fee payment: 12